Vat dye and intermediate



Patented Aug. 11, 1953 UNITED STATES PATENT OFFICE VAT DYE AND INTERMEDIATE Wilhelm schmidteNickels, Little York, N. 3., as-. signer to General Aniline & Film Corporation, New York, N, Y., a corporation of Delaware No Drawing. Application March 19, 1951, sfllfial No. 216,457

2 Claims.

1 This invention relates to new and valuable vat d es uf c ta n ng a b nzan hro e nuc eu a intermediates therefor and particularly to dyest fis ont n a be zan hr ne n cleus. r a

ed with a thionaphthene to form a fast bright said compounds being unsubstituted or alkyl (methyl, ethyl, propyl') substituted or, by further substitution, containing .one or more nuclear substituents of the class consisting of halogen (chlorine, bromine), .alkoxy (methoxy, ethoxy), and acylamino (benzoylamino) groups.

The dyestuffs of this invention are prepared by reacting equal molar proportions of thionaphthene and benzanthrone Bzi-carboxylic acid chloride in the presence of anhydrous aluminum chloride in a solvent such as nitrobenzene. The resultant compound is then ring-closed by aluminum chloride-sodium chloride fusion in presence of oxygen. The first reaction is carried out at a temperature in the range to 100 C. and preferably in the range to C. The fusion may be accomplished at a temperature of about -190 and preferably 170 C. The

time of the first reaction is several hours while the aluminum chloride-sodium chloride-oxygen treatment takes only about 45 minutes. The dyestuffs obtained dye cotton and other cellulose fibers a bright orange in the usual vat dye pro'c ess to shades having excellent iastness to chlo rine bleach. 7

A preferred method of preparing the dyestuffs of my invention is illustrated by the following example, wherein parts are by weight, but it will be understood that the invention is not limited theretoand that variations and substitutions may be made within the scope of the appended claims.

Example A charge of 108 parts nitrobenzene, 5.9 parts benzanthrone-Bz ecarboigylic acid chloride, 24 parts anhydrous aluminum chloride, 2.7 parts thionaphthene is stirred at 75-80" C. for 3 hours.

v The reaction product is poured into a little water containing 12 parts hydrochloric acidognoentrated (35%). The nitrobenzene is then removed by steam distillation. The solid reaction product is filtered and for removal of possibly present benzanthrone-Bzicarboxylic acid extracted at 70 C. with a mixture of 54 parts concentrated ammonia (28%) and 30.0 parts water. After filtration and washing to neutrality the product weighed 7.0 parts by weight.

The cyclizatign of the obtained ketone is carried out as follows: A charge of 107 parts anhydrous aluminum chloride, and 23 parts sodium chloride is heated to C. at which temperature there is added to the liquid melt under agitation 7 parts of the ketone. A fast stream of dry oxygen is blown through the melt under agitation at 160 C. for 45 minutes. The reaction product is poured into 500 parts water and 30 parts concentrated hydrochloric acid (35%). After boiling for 10 minutes the dyestuff is filtered, washed neutral and dried. Weight obtained equals 7 parts. A dyestufi past can be made by the known method of dissolving the dyestuff in concentrated sulfuric acid and pouring the solution in water. The

product dyes cotton from a hydrosulflte vat a bright orange shade of excellent chlorine fastness. Analysis: Found, S=8.81%; theory for C25H1202S, S=8.52%.

This reaction may be represented by the following scheme:

s n In AlCla nitrobenzene A1013 NaCl O2 to form:

Alternatively, the compound obtained by the example, unsubstituted or containing alkyl substituents may have other substituents introduced by the known procedures such as halogen, alkoxy and acylamino groups. Substituent alkyl groups in the original intermediates, of course, may not be present in position to block the reaction and ring closure (4 in the benzanthrone and 2,3 in the thionaphthene). It will be understood that such groups as halogen groups present in the original intermediates might not withstand the drastic conditions of the reactions and if these substituents are desired, they may be introduced after the dyestuif has been formed by procedures customarily used for introducing such substituents into vat dyestuffs of the benzanthrone series. 7 1 "1 If desired, bright orange vat dyestuffs of this invention can be converted into the alkali metal salt of the sulphuric acid ester of the corresponding leuco compound by the usual methods, for example, by reduction of the dyestuffs with a hydrogen liberating metal such as iron or zinc, preferably accompanied by a minor amount of copper, in a mixture of chlorsulfonic acid and pyridine followed by drowning of the reaction mixture in an aqueous alkali metal carbonate solution and salting out of the resulting leuco ester salt after removal of the pyridine by distillation. The resulting leuco sulphuric acid ester salts yield shades having color and fastness properties similar to those obtained by vat dyeing processes from the original dyestuffs, upon application by printing or dyeing of the material and development of the color by treatment with an acid oxidizing bath.

This is a continuation in part of my copending application Serial No. 77,440 filed February 19, 1949, now abandoned.

I claim:

1. A vat dyestufi having the following formula:

2. A process for preparing a bright orange vat dyestufi of the benzanthrone series which comprises reacting one mole of benzanthrone- Bzi-carboxylic acid chloride with one mole of thionaphthene at an elevated temperature and subsequently ring closing the ketone thus formed.

WJLHELM SCHMIDT- NICKIijLS.

N refer nces c t d. 

1. A VAT DYESTUFF HAVING THE FOLLOWING FORMULA: 